Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
  • C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
  • C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/02—Ortho- or ortho- and peri-condensed systems
  • C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
  • C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
  • C07C2603/50—Pyrenes; Hydrogenated pyrenes

Definitions

• the invention relates to new mercaptopyrenes, their production and their use for the production of electrically conductive salts (charge transfer complexes) of mercaptopyrenes.
• the charge transfer complexes are referred to below as CT complexes).
• CT complexes The invention further relates to the CT complexes of mercaptopyrenes.
• CT complexes which contain three or more mercapto groups in the pyrene molecule can easily be oxidized to salts (CT complexes) and that these CT complexes have very good electrical conductivity, high stability and good processing properties.
• CT complexes tetracyanoquinodimethane (TCNQ), tetrathiafulvalene and bisethylenodithio-tetra-thiafulvalene
• TCNQ tetracyanoquinodimethane
• tetrathiafulvalene and bisethylenodithio-tetra-thiafulvalene the CT complexes obtainable from the mercaptopyrenes according to the invention represent a new interesting alternative because of their easier accessibility, higher stability and improved processability.
• n is an integer from 3 to 10, preferably 3 or 4
• R represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl or aryl radical, preferably a C1-C12 alkyl radical.
• R for example: as optionally substituted alkyl radicals C1-C22-alkyl radicals such as methyl, ethyl, n- and i-propyl, n-, sec- and tert-butyl, 2-ethyl-hexyl, n-dodecyl -, Palmityl, stearyl and behenyl radical and substituted by halogen, hydroxy, C1-C4-alkoxy, nitro, cyano, carboxy, C1-C4-alkoxycarbonyl, acyl or amino C1-C12-alkyl radicals such as the 2- Chlorine, 2-bromo, 2-hydroxy, 2-methoxy, 2-cyanoethyl radical, the trifluoroethyl, trichloromethyl, carboxymethyl, ethoxycarbonylmethyl, benzoylmethyl radical; as optionally substituted alkenyl radicals, especially the allyl and oleyl radical; the proparg
• R are optionally substituted by C1-C4-alkyl, C1-C4-alkoxy and / or halogen C1-C22-alkyl, benzyl and phenyl radicals.
• the mercaptopyrenes of the formula I according to the invention are obtained by reacting halopyrenes of the formula in the n has the meaning given under formula (I) and Hal represents halogen, preferably chlorine or bromine, with mercaptides of the formula K m (SR) m (III), in the R has the meaning given under formula (I) and K m stands for an m-valent cation, preferably an alkali or alkaline earth ion, in a strongly polar, aprotic organic solvent at temperatures from 0 to 150 ° C., preferably 20 to 150 ° C.
• the invention therefore also relates to a process for the preparation of the mercaptopyrenes of the formula I, which is characterized in that halopyrenes of the formula II with mercaptides of the formula III in a strongly polar, aprotic organic solvent at temperatures from 0 to 150 ° C., preferably 20 up to 150 ° C.
• halopyrenes of the formula II and their preparation are known (see, for example, DE-OS 3 532 882 and Liebigs Ann. Chem. 531 , 2 ff (1937).
• the mercaptides of formula III can be used as such or in situ in the reaction mixture from the corresponding mercaptans and bases, e.g. Sodium hydride or sodium methylate are generated.
• aprotic solvents are dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-methylcaprolactam, tetramethylene sulfone, ethylene carbonate, propylene carbonate, N, N'-dimethylimidazolidinone and tetramethylurea.
• the mercaptopyrenes of the formula I according to the invention can be oxidized chemically or electrochemically to give electrically conductive salts (CT complexes); the composition of these CT complexes can be determined by the formula describe in the R and n have the meaning given under formula I, x indicates the total number of neutral and charged mercaptopyrene units contained in a 1-valent mercaptopyrene cation and is an integer or fractional number from 1 to 10, preferably 1 to 5, A ⁇ stands for an anion and y is the number of negative charges (i.e. the negative valence) of the anion and the number of 1-valent mercaptopyrene cations required to neutralize these negative charges and is an integer from 1 to 3, preferably 1.
• anions come monovalent anions such as Cl ⁇ , Br ⁇ , J ⁇ , J3 ⁇ , HSO4 ⁇ , the methosulfate, tosylate, perchlorate, tetrafluoroborate or hexafluorophosphate ion, but also divalent ions such as the sulfate and trivalent ions such as that Phosphate ion into consideration.
• Monovalent anions such as methosulfate, hexafluorophosphate, tetrafluoroborate, perchlorate, J3 ⁇ -, Br3 ⁇ - and the tosylate anion are preferred .
• the mercaptopyrenes according to the invention can be oxidized either electrochemically or chemically.
• the electrochemical oxidation is carried out in inert solvents in the presence of conductive salts.
• nitriles such as acetonitrile, propionitrile and butyronitrile
• Amides such as dimethylformamide and dimethylacetamide, ureas such as tetramethylurea, carbonates such as 1,3-dioxa-cyclohexanone- (2) and 1,3-dioxa-4-methyl-cyclopentanone- (2)
• Lactones and lactams such as butyrolactone and N-methyl-pyrrolidone and caprolactam
• Sulfoxides and sulfones such as dimethyl sulfoxide and dimethyl sulfone and tetramethylene sulfone
• aromatic hydrocarbons such as toluene, xylene and chlorobenzene, ketones such as acetone or cyclohexanone
• Alcohols such as methanol and ethanol
• halogenated hydrocarbons such as methylene chloride and 1,2-dichloroethane
• conducting salts are the fluorides, chlorides, bromides, iodides, monoalkyl sulfates, perchlorates, tetrafluoroborates, hexafluorophosphates, hexafluoroantimonates, hexafluoroarsenates, methanesulfonates, trifluoromethanesulfonates, benzenesulfonates, tosylates, benzoates and acetates of alkali and alkaline earth metals or of copper and silver, further from Onium compounds used which were obtained by exhaustive alkylation of arsines, phosphines, thioethers or tertiary amines.
• onium salts can be used directly in the form in which they are obtained in the exhaustive alkylation.
• the anion can first be exchanged for another anion, for example in tetrabutylammonium chloride, the chloride ion for tetrafluoroboration.
• the electrochemical oxidation is carried out at temperatures from -78 ° C to the boiling point of the solvent used. Temperatures from 0 to 100 ° C., in particular from 20 to 85 ° C., are preferred.
• concentrations of mercaptopyrenes in the solutions to be electrolyzed are between 0.001 mol / l and the saturation concentration of the mercaptopyrene in question in the respective solvent at the temperature used. Concentrations of 0.005 to 0.02 mol of mercaptopyren per liter of solution are preferred.
• the conductive salts can be used in a two to twenty-fold molar excess, based on the mercaptopyrene used. 3 to 12 moles of conductive salt per mole of mercaptopyrene are preferably used.
• the electrochemical oxidation can be carried out potentiostatically or galvanostatically.
• the galvanostatic mode of operation is preferred.
• electrolysis is carried out in a 100 ml cell with two 16 cm 2 Pt electrodes arranged at a distance of 1 cm at a current of 1.5 mA and a cell voltage between 0.7 and 5 V. If necessary, the anode and cathode compartments can also be separated by a membrane or frit.
• CT complexes of mercaptopyrene according to the invention are scheduled at the anode during electrolysis and are mechanically known in a manner known per se Separation, washing with one of the inert solvents mentioned above and drying obtained by analysis.
• the mercaptopyrenes according to the invention are reacted with customary oxidizing agents.
• the amount of oxidizing agent is measured so that 0.1 to 5 equivalents of oxidizing agent are used per mole of mercaptopyrene.
• the number "x" can be influenced which affects the total number of mercaptopyrene units contained in the 1-valent mercaptopyrene cation. The lower the amount of oxidizing agent, the greater the number of neutral mercaptopyrene units in the mercaptopyrene cation.
• the mercaptopyrenes according to the invention are oxidized in the presence of liquid diluents.
• the mercaptopyrenes can be completely or partially dissolved or only suspended in this liquid medium.
• both the oxidizing agents commonly used for chemical oxidations of chemical compounds such as H2O2, Caro's acid, perborates, peroxydisulfates, perbenzoic acid, ozone, halogens such as chlorine, bromine or iodine, potassium permanganate, potassium chromate, potassium dichromate, are suitable ; for the oxidative polymerization rocyclic compounds to electrically conductive polymers used oxidizing agents such as iron (III) salts such as Fe (III) chloride, Fe (III) tosylate, Fe (III) perchlorate, Fe- (III) -4-dodecylbenzenesulfonate , also nitronium hexafluorophosphate, arsenate, antimonate, nitronium tetrafluoroborate, nitrosonium hexafluorophosphate, arsenate, antimonate,
• Organic solvents which have the best possible dissolving power for the mercaptopyrene are preferably used as diluents.
• the chemical oxidation is carried out at temperatures from 0 to 200.degree. C., preferably in the range from 0.degree. C. to the boiling point of the solvent used;
• the CT complexes obtainable by the oxidation of the mercaptopyrene according to the invention are valuable organic, electrically conductive compounds. They are suitable for the antistatic treatment of plastics and as organic conductors in the electronics sector for the transmission of electrical signals and electrical energy.
• Example 1 a In the reaction vessel described in Example 1 a), the suspension of 12 g (0.4 mol) of sodium hydride (80% in paraffin) in 100 ml of 1,3-dimethylimidazolidinone-2 at 0 ° C slowly mixed with 24.8 g (0.4 mol) of ethyl mercaptan. 25.9 g (0.05 mol) of 1,3,6,8-tetrabromopyrene are then added to the reaction mixture with stirring. The reaction mixture is stirred for 1 hour at room temperature and for 24 hours at 40 ° C. The yellow precipitate is then filtered off, washed with water and methanol and dried in vacuo at 100 ° C. for 1 hour.
• a solution of 1 mmol was placed in a 100 ml electrolytic cell equipped with two 16 cm2 Pt electrodes (distance between the electrodes: 1 cm) Tetramethylmercaptopyren and 5 mmol of conductive salt in 100 ml of nitrobenzene at a current of 1.5 mA electrolyzed.
• the table below summarizes the mercaptopyrene-CT complexes obtained, the conductive salts used for the oxidation, the electrolysis time and temperature used and the electrical conductivities of the CT complexes (powders) and the yields in which they were obtained.
• CT complex of the formula preserved in the form of fine, matted, black and gold crystal needles.
• the electrical conductivity of the CT complex is 8.7 S / cm, its decomposition temperature is 240 ° C.
• CT complex of the formula obtained in the form of an olive green crystal powder.
• the electrical conductivity of this CT complex is 3 x 10 ⁇ 3 S / cm; FP .: 106-108 ° C.
• the conductivity of the complex is not affected by the melting.
• the electrical conductivity of the crystals is 3.2 S / cm.
• CT complex of the formula obtained in the form of dark crystals with a gold metallic sheen.
• the electrical conductivity of the CT complex is 0.3 S / cm.
• the electrical conductivity of this CT complex is 0.16 S / cm.
• the complex melts at 120 ° C with the release of iodine vapors.
• CT complex of the formula obtained in the form of a black crystal powder.
• the conductivity of the CT complex is 5.1 x 10 ⁇ 2 S / cm; FP .: 230 ° C (under deflagration).
• CT complex of the formula obtained in the form of a black crystal powder.
• the electrical conductivity of the CT complex is 1.25 S / cm; FP .: 270 ° C (with decomposition).

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• 1988
  • 1988-04-29 DE DE3814534A patent/DE3814534A1/de not_active Withdrawn
• 1989
  • 1989-04-10 US US07/335,902 patent/US5008430A/en not_active Expired - Fee Related
  • 1989-04-17 EP EP19890106821 patent/EP0339419A3/fr not_active Withdrawn
  • 1989-04-24 JP JP1101834A patent/JPH0211560A/ja active Pending

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